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Maize (Zea mays L., hybrid INRA 260) was grown in the greenhouse with mineral nutrition of different sulphate concentrations. Mature seeds from these plants were compared for their free amino acid and protein N forms. For the most S‐deficient sample, the Asx (asparagine + aspartic acid) content increased by 30% as compared with control, while methionine and cysteine decreased (by 25 and 30%, respectively), as well as glycine, lysine, histidine, arginine and tryptophan. In seeds lowest in S the non‐protein N to total N ratio was 77% higher than in the control. Free asparagine dominated in starved seeds (50 mol % of total free amino acids) and was ten‐fold more concentrated than in the control, where proline was the predominant free amino acid. Thus the Asx of non‐protein N reached 28% of the total mol Asx of the whole starved seed. Altered S nutrition had virtually no effect on the amino acid composition of the main protein fractions, but it significantly changed their ratios. Zeins, which are poor in S‐containing amino acids, showed 25% higher level than in seeds supplied with normal S. As a counterbalance, two glutelin subfractions rich in S‐containing amino acids, decreased by 36–71% under limiting S nutrition. It is concluded that the plant reacts against S deficiency by modifying its N metabolism. Significant accumulation occurred of free asparagine, which is the main form of N transportation. The biosynthesis of seed storage protein occurred through the accumulation of the highest possible protein quantity allowed by the available S‐containing amino acids, i.e. proteins low in S‐containing amino acids were preferentially synthesized.